Hydrocarbon oil conversion



June 19, 1934. J. G. ALTHER HYDROOARBON OIL CONVERSION Filed Deo. 11, 1930 patented June 19, 1934 1,963,605

nvnnocAnBoN on. coNvEnsroN Joseph G. Alther, Chicago, Ill., assigner to Universal Oil Products Company, Ultimo, nl

a corporation of South Dakota application Dember 11, 1930, serai Nag 501,506

v claims. (ci. 19e-4s) y This invention relates to the treatment of hythrough line 12vinto heating element 13 disposed drocarbon oils and .refers more particularly tov in a. suitable furnace setting 14. If desired,l the the conversion of hydrocarbon oils into `lower loil may be pumped directly into the heating eleboiling products of a more valuable character, ment 13 through lines 10 and 12 controlled by 5- such as the production of motor fuels of high valves l0 and 11. 'Ihe purpose of indirect heat 55 anti-knock value. exchange in the fractionator or of directly charg- One of the most diflicult problems facing the ing the oil into the heating element is to prevent rener of y certain types of oils such as Pennsylvaporization of some of the lower boiling comvania and Muskegon crude oil, is the low antiponents of the charging oil before subjecting l knock value' of the gasoline which occurs natthem to conversion conditions, as these com- 00 urally in the crude oils from these `respective ponents would be collected with the low boiling districts. product of the process and reduce considerably From an economic view point, my invention the anti-knock properties of the product.

provides a process which permits the reiiner to The oil at conversion conditions may be dis- `1:, convert intermediate boiling vfractions above the charged through line 15v controlled by valve 16 65 boiling range of gasoline into high yields of antiinto the reaction chamber 17. The unvaporized knock motor fuel, which in addition to the ad-r residue together with vapors and gases may be vantages per se permits the reflner to utilize the discharged through line 18 controlled by valve product of my invention as a blending agent to 19 and passed into the vaporizing chamber 21.

20 increase the anti-knock value of the straight run A small portion of the vapors with accompany- 70 motor fuel produced from the same or similar ing gases may be 4withdrawn through line 22 stock, thus facilitating its sale and making its controlled'by valve 23 and introduced directly use more desirable. into the fractionator' to assist in reboiling the vIn one of its speciiic embodiments the invenreflux condensate therein and to separate any tion provides a process which comprises subjectgases y which may' possibly become segregated 75 ing hydrocarbon oils to heat treatment at confrom the vapors in chamber 17. The non-vaversion conditions, introducing the heated oil porized residue may be withdrawn from chamber into an .enlarged reaction zone, removing the 21 through line 24 controlled by valve 25. The total products comprising the non-vaporized oil vapors leaving the chamber 21 may pass through together with vapors and gases and introducing line 26 controlled by valve 27 and into the fracgn thevsame into a vaporizing zone, separately wthtionator 6 wherein the vapors are fractionated.

drawing the non-vaporized oil from the vapors The reflux condensate from the fractionator 6 and gases, returning the reflux condensate from passes through line 28 controlled by valve 29 and the fractionating zone to the heating zone for is pumped by means of pump 30 through line further conversion, subjecting the vapors to. 31 controlled by valve 32 and through line` 12 33 fractionation, and subsequently cooling, con' into the heating element 13, where it may be densing and collecting them. subjected to cracking conditions for further con- The accompanying diagrammatic drawing version into lower boiling products. shows one form of apparatus suitable for carry- The -vapors leaving the fractionator 6 pass .40 ing out my invention. through line 33 controlled'by valve 34 and through 90 Referring in detail to the drawing, raw oil cooler and condenser 35 controlled by valve 36, charging stock may be introduced through line 1 the condensed vapors being collected in receiver controlled by valve 2 and may be pumped by 37. Gases may be withdrawn from receiver 37 means of pump 3 through lineA 4 controlled by through line 38 controlled by valve 39, which valve 5 into the fractionator 6, where it may may also function as a pressure control 95 preferably be brought into indirect heat exvalve upon the entire system or various change with the vapors arising therein by means parts thereof. The liquid accumulating in reof heat exchanger 7. The oil continues in its ceiver 37 may be withdrawn through line 45 concourse through line 8 controlled by valve 9, trolled by valve 46. Aportion of the condensate through line 10 controlled by valve 11 and may be returned'through line 40 controlledby valve 41 and pumped by means of pump 42 through line 43 controlled by valve 44 into the fractionator 6, where it serves to assist in cooling the vapors arising therein and to control the fractionation thereof.

In some cases in order to overcome operating diculties such as possible coking of the line 18, I have found it desirable to introduce suitable cooling oils from an external source, the arrangement for which is not shown but will be obvious to those skilled in the art.

` In the operation of the process it is desirable to maintain substantially no liquid level in the reaction chamber 17, the hydrocarbon material undergoing reaction in the chamber being substantially in the vapor phase. The arrangement is such as to cause the hydrocarbon vapors to traverse substantially the entire length of the reaction zone, the main purpose of which is to obtain the longest possible reaction time upon all of the hydrocarbon vapors in the reaction zone and to prevent short-circuiting of a portion of the hydrocarbon vapors. This permits maximum conversion and homogeneous treatment of the hydrocarbons undergoing conversion. The ternperature and pressure conditions employed may Vary over a Wide range and uniform or equalized pressures may be used throughout the system, or differential pressures may be employed on the various elements thereof, varying from sub-atmospheric to high super-atmospheric pressures. Preferably relatively highsuper-atmospheric pressures may be employed on the conversion elements and relatively low pressures employed on vaporization, fractionating, condensing and receiving elements.

obtained by the operation of the process of my invention:

Analysis of raw oil Charging stock 8@ Anaylses of products Pennsylvania kerosene distl' la un No. 1 Sample P 10Q ress. DBL Reflux Resid.

A. P. I. Gr. 61. 9 30. 9 12. 2 I. B. P. F 92 350 348 E. P. F 373 7 758 Flash point (Cleveland) F 145 105 Fire point (open cup) F 190 Flash point (PenskyMartens) l,171. 100

Furol viscosity 122 F.. Cold test F B.S. and W Percent over:

1o While my process is suitable for the treatment gg" of hydrocarbon oils of both low and relatively 401:: high boiling ranges, comprising residual fuel oils, gmtopped crude oils, gas oils, kerosene distillate, 7012" naphthas, including the reforming of gasoline, it has proven highly suitable for the treatment of 95: relatively low boiling or high gravity charging ,y E- 758 @recovery 84.0 stocks; for example, Pennsylvania distillates vacoke ly weight- 16,5 rying in gravity from 36 to 46 A. P. I. Zglg. 11" 122g g 120 The following results which are illustrative 512 ggg 4510 only are given as examples of actual results benzol eqmvaent 57 Pennsylvania kerosene distillate- Run No. 2 Run No. 3

Sample Press. dist. Redux Resid. Press. dist. Reux Resid.

A, 61.4 28.4 I. 94 357 E. P. F 383 Flash point ev Fire point (open cup) F... Flash point (Pensky-Martens) Furol viscosity 122 F 13 135 Cold test F %B, sandw Percent over- E. P. recovery a coke by weight 410 572 F benzol equivalent C) Not reported.

It isk obvious from 'one results obtained, both in regard to yields and high anti-knock properties of distillate being forced through the heating zone, removing the vapors remaining uncondensed afloo ` ronmyxvmmkmmdmmmnv Run No. 4 Run No. 5

Sample Pxossnist Reflux Resid. Promdist. Redux Resid.

61.0 8.o e241 am v:5.o .iii 9o 3a 81 w au E. P. F 384 775: 374 740 735; Flash point (Cleveland) F' z 150 165 Fire point (open cup) "F x, 200 m5 Flash pomo (Ponen-Martens) r g 13o 14o; Furol viscosity 122 F g 13'; 18 agioa o o Perceit over-v- TempgF. 5 TempF Templ. TempioF. Templi?.

s is i :si ze i: s n a a eo 2st soo 27o 482 7n aos 'E 722 292 51o 'E' oso 235.1 384 775 374 74o 735 %reoovery 92.0 o 86.5 94l0 97.5 75% itoyow Z (om it. 2%5 ses F1 si r2 '72 equivalent 61 l 63 Not reported.

Another ser. or examples are given be1ov. the prodtwh;speilallr vtvlilole colcisidrsehe source o pr u c, ave c os a Pennsylvania kerosene highly useful process of broad scope and it .is

distillatol intended that the examples given are to be i1- y v lustrative only and are not restrictive of the broad non Run non mm Run principles of the invention. N 1 No' 2 N0* 3 N- 4 N 5 Kerosene distillate as used herein is intended to dene a hydrocarbon distillate product winch essure= 5o has a boiling range substantially within the iraatam3r:zzz 325g it angedo atntigolgcglmg point of 300 r., and o n n o g 43g gg While I have illustrated the invention specically used in kerosene distillate of Pennsylvania (g3 32(2) 3% 3g?, 3g?, origin, it is to be understood that the invention 50 ooo 97o seo 981 is not to be limited to the use only of kerosene O 977 984 99 100 distillate from Pennsylvania. Kerosene distil- 920 seo 94o 94s 960 lates of any origin are contemplated for treatg $2 gg) g2?, ment according to the present invention under 90o on 92o 93o ses equivalent conditions to those speeiiied in the ilm 777 787 w1 817 lustrative runs for obtaining equivalent results. m 71a 722 7a2 14e I claim as my invention: Y 70 705 708 m 731 1. A process for converting kerosene distillates oas o45 ce1 eee 684 into liquid products of lower boiling Point range, 2g 22?; gg which comprises forcing a stream of such distillate mtemperatures through a heating zone and raising it to a con- Rgtafgdclgifntlf; um 27 36 115 n version temperature, discharging said heated To 925 en 95s 1004 1032 products from the heating zone into the upper Si?, 32,15 gg portion of an enlarged vertical reaction zone, withdrawing substantially all of the products of couple mba@ order, reaction from the lower portion of said reaction zone and discharging same into an enlargedseparating zone wherein vapors separate frommen- Pennsyvama me distmvaporous residue, subjecting the vapors separated in said separatingzone to fractionation in a frac- 1 2 3 i 4 5 tionating zone, removing from an upper portion of said reaction zone a relatively small proportion g) Ireuxftgiggsairflv 011-- 3-0 3.2 M5 2.7 28 of the gaseous and vaporous products of reaction eoig Gig 7gg gg gli?! gig anlciti dischargiinfg same Sirecyeintjthmlwler @S1 po on o sa. rac lona mg n su ec e (a) GBIQSS who!" Bas am" 252 ,22's 27'? 2M 3.22 vapors in said fractionating zone to fractionation Cudtperbblchar9- 621 715 769 769 875 to condense the heavier fractions thereof as re- S31 giilgo g1g 1?, iux condensate, removing said reux condensate and admixing same with the stream of kerosene ter passage through the fractionating zone and condensing and collecting the distillate resulting therefrom as the product of the process.

2. A. process for converting kerosene distillates into liquid products of lower boiling point range, which comprises forcing a stream of such distillate through a heating zone and raising it to a conversion temperature, discharging said heated products from the heating zone into the upper portion of an enlarged vertical reaction zone, withdrawing substantially all of the products of reaction from the lower portion of said reaction zone and discharging same into an enlarged separating zone wherein vapors separate from nonvaporous residue, removing the residue from said separating zone and isolating same from the system, subjecting the vapors separated in said separating zone to fractionation in a fractionating zone, removing from an upper portion of said reaction zone a relatively small proportion of the gaseous and vaporous products of reaction and discharging same directly into the lower portion of said fractionating zone, subjecting the vapors in said fractionating zone to fractionation to condense the heavier fractions thereof as reflux condensate, removing said reflux condensate and admixing same with the stream of kerosene distillate being forced through the heating zone, removing the vapors remaining uncondensed after passage through the fractionating zone and condensing and collecting the distillate resulting therefrom as the product of the process.

3. A process for converting kerosene distillates into liquid products of lower boiling point range, which comprises forcing a stream of said kerosene distillate through an elongated passageway exposed to heat and raising said distillate to a cracking temperature, discharging said heated stream into the upper portion of an enlarged vertical reaction zone, maintaining superatmospheric pressure in said elongaed passageway and in said reaction zone, removing substantially all of the vaporous and liquid products of reaction from the lower portion of said Zone and discharging same into a zone of reduced pressure wherein vapors separate from non-vaporous residue, drecting said separated vapors to a fractionating zone, removing from an upper portion of said reaction zone a relatively small proportion of the gaseous products of reaction and discharging same directly into the lower portion ci said fractionating Zone, subjecting the vapors in the fractionating zone to fractionation to condense the heavier fractions thereof as reiiux condensate, removing said reflux condensate and adrnixing same with the stream of kerosene distillate being forced through the elongated passageway in the heating zone.

d. A hydrocarbon oil cracking process which comprises passing the oil in a restricted stream through a heating zone and heating the saine `therein to cracking temperature under pressure,

discharging the heated oil directly from the heating zone into the upper pordon of an enlarged vertical reaction zone maintained under cracking conditions oi temperature and pressure, passing the unvaporized oil and the maior portion of the vapors downwardly through said reaction zone and removing the same as a mixture from the lower portion thereof, the unvaporized oil being withdrawn from the reaction zone at such a rate that no appreciable liquid accumulation occurs therein, separately removing the remaining minor portion of the vapors from the upper portion oi? the reaction zone, discharging the mixtine withaccesos drawn from -the lower portion of the reaction zone into a separating zone maintained under lower pressure than. the reaction zone and separating the same therein into vapors and residue, introducing the thus separated vapors into a fractionating zone and dephlegmating the same therein to condense insufficiently cracked fractions thereof as reflux condensate, introducing said remaining portion of the vapors into the fractionating zone and contacting the same with reflux condensate formed therein, and nally condensing the vapors uncondensed in the fractionating zone.

5. A hydrocarbon oil cracking process which comprises passing the oil in a restricted stream through a heating zone and heating the same therein to cracking temperature under pressure, discharging the heated oil directly from the heating zone into the upper portion of an enlarged vertical reaction zone maintained under cracking conditions of temperature and pressure, passing the unvaporized oil and a major portion of Athe vapors downwardly through said reaction zone and removing the same as a mixture from the lower portion thereof, the unvaporized oil being withdrawn from the reaction zone at such a rate that no appreciable liquid accumulation occurs therein, separately removing the remaining minor portion of the vapors from the upper portion of the reaction zone, discharging the mixture withdrawn from the lower portion of the reaction zone into a separating zone maintained under lower pressure than the reaction zone and separating the same therein into vapors and residue, introducing the thus separated vapors into a fractionating zone and dephlegrnating the same therein to condense insumciently cracked fractions thereof as redux condensate, introducing said remaining portion of the vapors into the fractionating zone and contacting the same with reiiux condensate formed therein, returning reux condensate from the fractionating zone to the heating zone, and iinally condensing the vapors uncondensed in the fractionating zone.

d. A process for converting fuel oil into liquid products of lower boiling point range, which comprises forcing a stream of such oil through a heating zone and raising it to a conversion ternperature, discharging said heated products from the heating zone into the upper portion of an enlarged vertical reaction zone, withdrawing substantially all of the'products of reaction from the lower portion of said reaction zone and discharging san'ie into an enlarged separating zone wherein vapors separate from non-vaporous residue, subjecting the vapors separated in said separting zone to fractionation in a fractionating zone, removing from an upper portion of said reaction zone a relatively small proportion of the gaseous and vaporous products of reaction and discharging saine directly into the lower portion of said fractionating zone, subjecting the vapors in said iractionating zone to fractionation to condense the heavier fractions thereof as reflux condensate, removing said reflui; condensate and admixing saine with the stream of fuel oil being forced through the heating zone, removing the vapors remaining uncondensed after passage through the fractionating zone and condensing and collecting the distillate resulting therefrom as the product or the process.

7. A process for converting gas oil into liquid products of lower boiling point range, which cornprises forcing a stream of such distillate through lll@ lllE

litt) a heatingzone and raising it to a conversion teml5@ perature, discharging said heated products from the heating zone into the upper portion of an enlarged vertical reaction zone, withdrawing substantially all of the products of reaction from the lower portion of said reaction. Zone and dischargi discharging same directly into the lower portion of said fractionating zone, subjecting the vapors in said fractionating zone to fractionation to condense the heavier fractions thereof as reflux condensate, removing said reux condensate and admixing same with the stream of gas oil being forced through the heating zone, removing the vapors remaining uncondensed after passage through the fractionating zone and condensing and collecting the distillate resulting therefrom as the product of the process.

' JOSEPH G. ALTHER. 

